Phenol-modified resins from crude solvent naphtha



Patented June 13, 1939 PATENT OFFICE- PHENOL-MODIFIED RESINS FROM CRUDESOLVENT NAPHTHA William H. Cal-mods, Pittsburgh, Pa., assignor to TheNeville Company, Pittsburgh, Pa" a corporation of Pennsylvania NoDrawing. Application January 21, 1938, Serial No. 186,140

3 Claims. (01. 260-91) This invention relates to improvements inphenol-modified resins produced from crude solvent naphtha, especiallyphenol-modified coumarone resins, and it is among the major ob-' 5 jectsof the invention to improve certain properties of such resins to renderthem more useful in the arts and without substantial depreciation of thedesirable properties which they inherently possess.

Crude solvent naphthas produced, for example,

in the by-product coking of coal, contain polymerizable constituentswhich may be predominantly of the coumarone-indene type, or of thedicyclopentadiene type, according to the proximate source from which thenaphthas are derived. Procedures for effecting the polymerization ofthose materials into useful resins are .known and used in the art, forwhich reason they need not be specifically detailed herein. Al-

though the resins produced possess various properties which render themespecially desirable for uses to which resins are put, these resins arecharacterized by substantial insolubility in the solvent alcohols usedcommercially, although alcohol solubility can be conferred by phenolicinvolvement, or modification, of the resins during polymerization.

r A procedure for phenolic modification of these resins is described inGerman Patent No. 302,543, a and improved procedures for accomplishingthis are described and claimed in Patent No. 2,077,009 to JosephRivekin, granted April 13, 1937, and in a copending application SerialNo. 89,847,'filed July 9, 1936, by Joseph Rivkin. In accordance with theprocedure of Patent No. 2,077,009 to Joseph Rivkin phenol-modified resinis produced by polymerizing the polymerizable constituents of crudesolvent naphtha in the presence of a phenolic substance, such ascresols, phenols, 40 naphthols, and the like, which is reactive with theresin-forming constituents. In thepractice of that invention thepolymerization is eii'ected by means of activated clay and withmoderately elevated temperature, for instance in the neighborhood of 100C., the reaction body being agitated during the course-of the reaction.

In accordance with the invention of the aforesaid application Serial No.89,847, the phenolic involvement is achieved through the conjoint use ofa sulfuric acid base catalyst and of phenolic reagent in a quantity byweight notless than about 22 per cent of the weight of the polymerizableconstitutnets of the crude solvent naphtha.

' During the progress of the reaction the liquid body is agitated andits temperature is maintained below about 0., most suitably within therange 25 to 35 C. The term sulfuric acid base catalyst" is used to referconcisely to concentrated sulfuric acid or derivatives of sulfuric acidobtained by the substitution of at least one 5 hydrogen atom or onehyroxyl group of the sulfuric acid by an aliphatic or an aromatic groupwhich may, in turn, be substituted by other groups, such as hydroxylgroups, amine groups. and the like. This latter procedure results, in 10general, in products having a lower acid number than characterizes thephenol-modified resins produced in accordance with the procedure of theaforementioned patent.

It is characteristic of all of these resin prod- 15 ucts that theypossess to a marked extent solubility in alcohol, and particularly isthis true of the phenol-modified resins made in accordance with theaforesaid inventions, which are also compatible with cellulose nitrate.-By virtue of 20 these properties these phenol-modified resins are suitedto commercial uses requiring resins having such characteristics. Forinstance, the alcohol solubility of these resins not only permits theiruse in making varnishes, but the phenolic 25 involvement additionallyserves in, some manner to inhibit-gas checking during the drying of avarnish film comprising such resin, as disclosed and claimed in PatentNo. 2,094,331, granted September 28, 1937, to Joseph Rivkin. Likewise,30 the compatibility of resins produced according to the aforesaidinventions renders their use possible with cellulose nitrate in makingplastics and other products therefrom.

Despite the desirable properties of such resins, 35 such as theirresistance to dilute acids and alkalies, good film-formingcharacteristics, compatibility with cellulose nitrate, solubility inalcohols,

and others, these phenol-modified resins as produced heretofore havebeen unsuited to certain 40 uses because in general they are ratherstrongly colored and possess a distinctive odor which may beobjectionable for some purposes. I have discovered, and it is upon thisthat the present invention is predicated, that these undesirable 45properties of phenol-modified solid resins resultant from cmde solventnaphtha may be diminished or eliminated without materially depreciatingthe desirable properties inherent in such resins, by hydrogenation ofthe resin. In other 50 words, I have discovered that by hydrogenation ofthe normally solid phenol-modified resins, the color and odor may beimproved, even to the point where the hydrogenated product issubstantially colorless and odorless, while the melt l6 ing point is notdecreased,-even with far-reaching hydrogenatiomthus insuring solid resinproduct.

In the practice of the invention the resin is dissolved in a suitablesolvent and the solution is subjected to hydrogen in the presence of aneffective hydrogenation catalyst, suitably under conditions of elevatedtemperature and pressure, the hydrogenation being carried out for suchperiod of time as to effect hydrogenation to the desired degree.

The following actual run is illustrative of the benefits to be derivedfrom and of the procedure used in the practice of the present invention.In this run there was used a phenol-modified coumarone-indene resinhaving a melting point of approximately 95 C. This had a color oi about3 on the customary resin scale, and it possessed a distinctive odor. Itssolubility in isopropyl alcohol was below 0. measured in the manner"customary in this art.

were placed in an autoclave together with 50 grams of Raney nickelcatalyst prepared in the manner known in the art. The autoclave was thenclosed and hydrogen gas was admitted to a pressure of 1050 pounds. Heatwas applied slowly to start the hydrogenation, and by the time thetemperature was 170 the pressure had dropped to 610 pounds, showingextensive hydrogenation. The pressure was then rebuilt, by introductionof hydrogen, to the original value,

.and when the pressure within the autoclave showed that the secondhydrogen charge had been nearly all absorbed the autoclave was rechargedto the initial pressure for the third time..

The color of the hydrogenated resin was less than V and the resin wassusbtantially odorless, while its melting point and specific gravitywere not changed appreciably. By treatment with alcohol the resinproduct could be separated into a portion which was insoluble and aportion which was completely soluble in the alcohol. The latter portionwas soluble in all proportions.

The invention resides broadly in my discovery that desirable propertiesare conferred upon these phenol-modified resins, without material detri-'ment to their inherently desirable properties, by

hydrogenation, and it is not restricted to any specific conditions ofhydrogenation. That is Fifty gramsof the resin and 80 cc. of petroleumbenzene the temperature and pressure may be related to eirect thedesired degree of hydrogenation. In general, the rate of hydrogenationwill increase with rise in temperature up to an optimum value whichgenerally is encountered somewhat below the temperature at whichdepolymerization will the process may be carried on at room temperature,especially if an eilicient catalyst is used. I

now prefer to use metallic nickel hydrogenation catalyst of theparticular type referred to hereinabove, but where tar-reachinghydrogenation is unnecessary, or for other reasons, other metallichydrogenation catalysts known in the art may be used, as will beunderstood by those skilled in the art.

In the preferred practice of the invention the phenolic involvement, forinstance as described hereinabove, is accomplished with a cresol such ascresylic acid of high boiling point.

According to the provisions of the patent statutes, I haveexplained theprinciple of my invention and have described what I now consider torepresent its best embodiment. However, I desire to have it understoodthat, within the scope of the appended claims, the invention described.

Iclaim:

1. As a new article of manufacture, a solid resin composed of polymersof the polymerizable constituents of crude solvent naphtha resultingfrom polymerization of said constituents with concurrent involvementwith a phenolic substance, and being further modified by hydrogenationand characterized by being substantially colorless and soluble inalcohols.

2. As a new article of manufacture, a solid resin composed oi polymersof the coumaroneindene constituents of crude solvent naphtha resultingfrom polymerization of said constituents withconcurrent involvement witha phenolic substance, and being further modified by hydrogenation, andcharacterized by being substantially colorless, odorless, and soluble inalcohols.

3. A product according to claim 2, said phenolic susbtance being acresol.

WILLIAM H. CARMODY.

'may be practiced otherwise than as specifically

